CA1096442A - No translation available - Google Patents
No translation availableInfo
- Publication number
- CA1096442A CA1096442A CA313,192A CA313192A CA1096442A CA 1096442 A CA1096442 A CA 1096442A CA 313192 A CA313192 A CA 313192A CA 1096442 A CA1096442 A CA 1096442A
- Authority
- CA
- Canada
- Prior art keywords
- electrochemical generator
- generator according
- electrolyte
- lithium
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000007773 negative electrode material Substances 0.000 claims abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract 4
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000004480 active ingredient Substances 0.000 claims description 7
- -1 tetrafluoborate Chemical compound 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011532 electronic conductor Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims 1
- 229910020355 Pb2Bi2O5 Inorganic materials 0.000 claims 1
- BTZNPZMHENLISZ-UHFFFAOYSA-N fluoromethanesulfonic acid Chemical compound OS(=O)(=O)CF BTZNPZMHENLISZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 241001676573 Minium Species 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 3
- 101100327917 Caenorhabditis elegans chup-1 gene Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XSQSCWZDPXWZSW-UHFFFAOYSA-N C1(OCC(C)CCO1)=O.C(O)(O)=O Chemical compound C1(OCC(C)CCO1)=O.C(O)(O)=O XSQSCWZDPXWZSW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
PRECIS DE LA DIVULGATION: Générateur électrochimique dont la matière active négative est le lithium, l'électrolyte une solution dont le solvant est un liquide aprotique et la matière active positive un dérivé de l'oxyde de plomb divalent PbO. Selon l'invention ledit dérivé est une combi-naison dudit oxyde de plomb avec un oxyde choisi dans le groupe des oxydes de bismuth Bi2O3, d'antimoine Sb2O3 et d'étain SnO2. On obtient ainsi des générateurs de grande énergie spécifique.PRECISE OF DISCLOSURE: Electrochemical generator whose negative active material is lithium, the electrolyte a solution whose solvent is an aprotic liquid and the positive active material a derivative of divalent lead oxide PbO. According to the invention, said derivative is a combination of said lead oxide with an oxide chosen from the group of oxides of bismuth Bi2O3, antimony Sb2O3 and tin SnO2. We thus obtain generators of high specific energy.
Description
~96fl~Z
La présente invention concerne les générateurs électrochimiques de grande énergie spccirique ayant cor~e matière active négative le lithium et comportant un électrolyte dont le solvant est un composé aprotique. El~e a plus spécialement pour objet la matière active positive de ces généra-teurs .
Le brevet français n 74 34 867 (publié sous le numéro 2 2~8 401)et son certificat d'addition n 75 20 497 (publié sous le numéro 2 316 756) ont décrit des piles au lithium dont la matière positive était oonstituée, entre autres, d'oxyde de plomb de formule Pb304, ou minium.
Au cours de ses recherches, la Demanderesse a constaté que oertains composés qui présentaient aveo le minium l'analogie de résulter de la combinaison d'un oxyde à caractère anhydride d'acide avec l'oxyde de plomb PbO qui a, lui, des caractères basiques, donnaient des résultats au moins égaux à ceux du minium, lorsqu'ils étaient employés comme matières actives positives dans les générateurs au lithium.
L'invention a donc pour objet un générateur électrochimique dont la matière active négative est le lithium, l'électrolyte une solution dont le solvant est un liquide aprotique et la matiere active positive un dérivé
de l'oxyde de plomb divalent PbO, caractérisé par le fait que ledit dérivé ~ 96fl ~ Z
The present invention relates to electrochemical generators high spcciric energy having cor ~ e negative active material lithium and comprising an electrolyte of which the solvent is an aprotic compound. El ~ e more specifically relates to the positive active material of these genera teurs.
French patent n 74 74 867 (published under number 2 2 ~ 8 401) and its certificate of addition n 75 20 497 (published under number 2 316 756) described lithium batteries of which the positive material was constituted, among others, lead oxide of formula Pb304, or minium.
During its research, the Applicant found that some compounds which presented with analogy the result of the combination of an oxide having an acid anhydride character with the oxide of PbO lead, which has basic characteristics, gave results less equal to those of minium, when used as materials positive active in lithium generators.
The invention therefore relates to an electrochemical generator of which the negative active ingredient is lithium, the electrolyte a solution of which the solvent is an aprotic liquid and the positive active material a derivative divalent lead oxide PbO, characterized in that the said derivative
2~ est une combinaison dudit oxyde de plomb avec un oxyde choisi dans le groupe des oxydes de bismuth Bi203, d'antimoine Sb203 et d'étain Sn 2 Le bismuthate de plomb de formule Pb2Bi205 a donné entre autres, d'excellents résultats. Cette matière active positive possède en outre sur le minium les avantages physiques suivants :
- sa poudre se moule parfaitement pour former des électrodes agglomérées, sans qu'il soit nécessaire d'y ajouter un liant comme dans le cas du ~inium.
- elle est beaucoup moins soluble dans le carbonate de propylène, entre autres, ce qui permet d'utiliser ce solvant d'électrolyte pour des piles qui doivent être conservées longternps.
Les électrolytes qui peuvent être utilisés dans les piles selon l'invention sont des solutions dont le solvant peut être un éther ou un ester ou des mélarl~es d~_ther~ e. d'esterls. Parmi ies éthers utllisables 1~964~2 peut citer le dioxolanne, le tétrahydrofuranne, le diméthoxyéthane ou leurs mélanges, et p?rmi les esters, le sulfite de diméthyle, le carbonate de propylène, le carbonate d'ethylène etc...
Le soluté est de préférence un sel de lithium, tel que le perchlorate, le tetrafluoborate, le rluorométhylsulfonate, l'hexa~luoroarséniate.
L'invention sera mieux comprise à l'aide des exemples suivants, illustrés par le dessin annexé dans lequel la figure 1 représente une coupe d'une structure de pile utilisable dans le cadre de l'invention et la figure 2 la décharge de deux piles, une pile de la technique antérieure et une pile selon l'invention.
On a préparé des piles de type bouton telles que celle repré-sentée sur la rigure 1, de diamètre extérieure 11,6 ~ et de hauteur totale 5,4 mm.
Le boitier se compose de deux coupelles 1 et 7 en acier nic'~elé, ou acier inoxydable, séparées par un joint 8 en matière plastique, ou élastomère, ... .
qui sert à l'étanchéité et à l'isolement électrique des coupelles entre elles. La coupelle négative 7 contient le lithium qui est 90US la forme d'une couche 5 incrustée sur un collecteur 6, constitué par une grille en acier nickelé, ou acier inoxydable, soudé à la coupelle. La coupelle positive 1 contient la matière active pulvérulente 2 qui est additionnée d'un conducteur électronique et, éventuellement, d'un liant. Cette masse active est comprimée dans la coupelle 1 qui peut comporter, ainsi que représenté, un anneau métallique 9 (en acier nickelé ou en acier inoxydable) qui sert à maintenir la matière active et à ren~orcer l'appui du joint 8 sur lequel est rabattue la coupelle 1.
Les matières actives positive et négative sont séparées par une barrière en papier 3 et des couches de feutre cellulosique 4 imbibées d'électrolyte.
1er exemple de réalisation, selon technique antérieure :
Une première série de piles à été montée sur le modèle décrit ci-dessus. La masse active positive se composait de minium pulvérulent auquel avaient été ajoutés du plomh pulvérulent et du polytétrafluvr~ithylene, l~s ~6~2 proportions respec~ives étant 73 ~, 23 ~ et 4 % en poids. L'ensemble de cette masse à été comprimé sous une pression de 1,5 tonne/cm2 dans la coupelle positive, la quantité introduite donnant une épaisseur de 1,35 mm à la masse cathodique. La capacité théorique est 148 mAh.
L'électrolyte est constitué par une solution 2M de perchlorate de lithium dans du dioxolanne. Ces piles représentent les piles de la technique antérieure.
Ces piles ont été déchargées sur une résistance de 5 000 ohms. La courbe A
de la figure 2 représente la courbe de décharge de ces piles, les tensions V, en volts1 ayant été portées en ordonnées et les temps de décharge T, en heures, en abscisses. Si l'on prend 1,2v comme tension d'arret le temps de décharge est d'environ 550 heures, ce qui correspond à une capacité
ef~e~tive de 1~5 mAh. Il faut cependant remarquer qu'aux tensions 1,3 a 1,2 volts il est très probable que le polytétraPluoréthylène participe à la déchdrge et qu'en conséquence le rendement est à attribuer à l'ensemble du minium et du polytétrafluoréthylène.
2ème exemple de réalisation, selon invention :
Une seconde série de piles semblables a été montée, mais avec une matière active positive selon la présente invention. Cette matière active se composait de bismuthate de plomb Pb2Bi205. On y a ajouté du plomb pulvé-rulent comme conducteur électronique, mais l'addition de liant est rendue inutile par les qualites de compressibilité de la poudre de bismuthate. La masse est alors plus conductrice que le mélange de minium et de polytétra-fluoréthylène et la quantité de plomb pulvérulent peut être abaissée à 10 ~.
La masse est donc à 90 % en poids de bismuthate, et 10 ~ de plomb métal.
La compression s'e~fectue à 1 tonne~cm2 pour obtenir la hauteur de 1,35 mm.
La capacité théorique de la masse ainsi obtenue est 198 mAh.
La courbe B de la figure 2 représente la décharge de ces piles sur une résistance de 5 000 ohms. Comme on le voit, bien que de dimensions exté-rieures égales à celles du premier exemple de réalisation, les piles decette série, utilisant la matière active positive selon l'invention ? se déchargent à une tension supérieure (1,45 volt de ten2ion moyenne, contre 1~:96~2 1,37 pour la première serie). Leur décharge dure 600 heures, ce qui correspond à une capacité de 175 mAh.
Bien entendu l'invention n'est nullement limit~e aux mode~ de réalisations décrits et représentés, qui n'ont été donnés qu'à titre d'exemples.
: 2 ~ is a combination of said lead oxide with an oxide chosen from the group of oxides of bismuth Bi203, antimony Sb203 and tin Sn 2 The lead bismuthate of formula Pb2Bi205 has given inter alia, excellent results. This positive active ingredient also has on the minimum the following physical benefits:
- its powder molds perfectly to form electrodes agglomerated, without the need to add a binder as in the case of ~ inium.
- it is much less soluble in propylene carbonate, among other things, which allows this electrolyte solvent to be used for batteries which should be kept longternps.
The electrolytes that can be used in batteries depending the invention are solutions in which the solvent can be an ether or a ester or melarl ~ es d ~ _ther ~ e. esterls. Among the usable ethers 1 ~ 964 ~ 2 may include dioxolane, tetrahydrofuran, dimethoxyethane or mixtures thereof, including esters, dimethyl sulfite, carbonate propylene, ethylene carbonate etc ...
The solute is preferably a lithium salt, such as perchlorate, tetrafluoborate, rluoromethylsulfonate, hexa ~ luoroarséniate.
The invention will be better understood using the following examples, illustrated by the appended drawing in which FIG. 1 represents a section of a stack structure usable in the context of the invention and the Figure 2 discharging two batteries, a battery of the prior art and a battery according to the invention.
Button type batteries such as the one shown felt on rigure 1, with an external diameter of 11.6 ~ and total height 5.4 mm.
The case consists of two cups 1 and 7 in nic '~ elé steel, or steel stainless, separated by a seal 8 made of plastic, or elastomer, ...
which is used for sealing and electrically isolating the cups between they. The negative cup 7 contains the lithium which is 90US the form a layer 5 embedded on a collector 6, constituted by a grid nickel-plated steel, or stainless steel, welded to the cup. The cup positive 1 contains the powdery active ingredient 2 which is added an electronic conductor and, optionally, a binder. This mass active is compressed in the cup 1 which can include, as well as shown, a metal ring 9 (nickel-plated steel or steel stainless) which serves to maintain the active material and to reinforce the support of the seal 8 on which the cup 1 is folded down.
The positive and negative active ingredients are separated by a paper barrier 3 and layers of cellulosic felt 4 soaked of electrolyte.
1st example of embodiment, according to prior technique:
A first series of batteries has been mounted on the model described below.
above. The positive active mass consisted of powdery minium to which had been added powdery plomh and polytetrafluvr ~ ithylene, l ~ s ~ 6 ~ 2 respec ~ ives proportions being 73 ~, 23 ~ and 4% by weight. All this mass was compressed under a pressure of 1.5 tonnes / cm2 in the positive cup, the quantity introduced giving a thickness of 1.35 mm to the cathode mass. The theoretical capacity is 148 mAh.
The electrolyte consists of a 2M solution of lithium perchlorate in dioxolane. These batteries represent the batteries of the technique anterior.
These batteries were discharged on a resistance of 5000 ohms. Curve A
of figure 2 represents the discharge curve of these batteries, the voltages V, in volts1 having been plotted on the ordinate and the discharge times T, in hours, on the abscissa. If we take 1.2v as the stop voltage, the discharge is approximately 550 hours, which corresponds to a capacity 1 ~ 5 mAh ef ~ e ~ tive. It should however be noted that at voltages 1.3 to 1.2 volts it is very likely that polytetraPluorethylene participates in the and therefore the return is to be attributed to the entire minium and polytetrafluoroethylene.
2nd embodiment, according to the invention:
A second series of similar batteries was fitted, but with a positive active material according to the present invention. This active ingredient consisted of lead bismuthate Pb2Bi205. Powdered lead was added to it.
rulent as an electronic conductor, but the addition of binder is made unnecessary by the compressibility qualities of bismuthate powder. The mass is then more conductive than the mixture of minium and polytetra-fluorethylene and the amount of powdery lead can be lowered to 10 ~.
The mass is therefore 90% by weight of bismuthate, and 10 ~ of lead metal.
Compression is carried out at 1 ton ~ cm2 to obtain the height of 1.35 mm.
The theoretical capacity of the mass thus obtained is 198 mAh.
Curve B in Figure 2 shows the discharge of these batteries on a 5,000 ohm resistor. As can be seen, although of external dimensions equal to those of the first exemplary embodiment, the batteries of this series, using the positive active material according to the invention? get discharge at a higher voltage (1.45 volts medium voltage, against 1 ~: 96 ~ 2 1.37 for the first series). Their discharge lasts 600 hours, which corresponds to a capacity of 175 mAh.
Of course, the invention is in no way limited to the mode of achievements described and represented, which have been given only as examples.
:
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7730946 | 1977-10-14 | ||
| FR7730946A FR2406312A1 (en) | 1977-10-14 | 1977-10-14 | SPECIFIC HIGH ENERGY ELECTROCHEMICAL GENERATORS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1096442A true CA1096442A (en) | 1981-02-24 |
Family
ID=9196497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA313,192A Expired CA1096442A (en) | 1977-10-14 | 1978-10-12 | No translation available |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4158723A (en) |
| EP (1) | EP0001598B1 (en) |
| JP (2) | JPS5935148B2 (en) |
| AU (1) | AU516528B2 (en) |
| BR (1) | BR7806748A (en) |
| CA (1) | CA1096442A (en) |
| DE (1) | DE2860549D1 (en) |
| DK (1) | DK458278A (en) |
| ES (1) | ES474185A1 (en) |
| FR (1) | FR2406312A1 (en) |
| IE (1) | IE47359B1 (en) |
| IT (1) | IT1108107B (en) |
| NO (1) | NO149299C (en) |
| NZ (1) | NZ188630A (en) |
| SG (1) | SG78683G (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207389A (en) * | 1977-11-25 | 1980-06-10 | P. R. Mallory & Co. Inc. | Solid state cells |
| FR2442515A1 (en) * | 1978-11-22 | 1980-06-20 | Accumulateurs Fixes | SOLID POSITIVE ACTIVE MATERIAL FOR SPECIFIC HIGH-ENERGY ELECTROCHEMICAL GENERATORS |
| JPS55157862A (en) * | 1979-05-25 | 1980-12-08 | Matsushita Electric Ind Co Ltd | Cell |
| JPS55165580A (en) * | 1979-06-11 | 1980-12-24 | Matsushita Electric Ind Co Ltd | Cell |
| US4301220A (en) * | 1980-06-24 | 1981-11-17 | Union Carbide Corporation | Nonaqueous cell with cathode comprising the reaction product of bismuth trioxide and molybdenum trioxide |
| US4302520A (en) * | 1980-06-25 | 1981-11-24 | Union Carbide Corporation | Cathode comprising the reaction product of bismuth, sulfur and lead or iron |
| US4419423A (en) * | 1980-06-27 | 1983-12-06 | Union Carbide Corporation | Nonaqueous cells employing heat-treated MnO2 cathodes and a PC-DME-LiCF3 SO3 electrolyte |
| US4298665A (en) * | 1980-06-27 | 1981-11-03 | Union Carbide Corporation | Cathode comprising the reaction product of Bi2 O3 and WO3 |
| FR2508239A2 (en) * | 1981-06-17 | 1982-12-24 | Gipelec | Electrochemical cell with cation conductive vitreous electrolyte - formed by powder compaction on cathode with lithium disc superimposed |
| JPS6060A (en) * | 1983-06-15 | 1985-01-05 | Mitsui Mining & Smelting Co Ltd | Positive electrode active substance for lead storage battery and battery utilizing said active substance |
| FR2547114B1 (en) * | 1983-05-30 | 1985-07-05 | Gipelec | POSITIVE ACTIVE MATERIAL FOR HIGH SPECIFIC ELECTROCHEMICAL GENERATOR |
| FR2550388B1 (en) * | 1983-08-03 | 1985-12-27 | Gipelec | POSITIVE ACTIVE MATERIAL FOR ELECTROCHEMICAL GENERATORS AND ELECTROCHEMICAL GENERATORS USING THE SAME |
| JPS6091565A (en) * | 1983-10-25 | 1985-05-22 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte battery |
| JPS6129072A (en) * | 1984-07-19 | 1986-02-08 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte cell |
| JPS6129071A (en) * | 1984-07-19 | 1986-02-08 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte cell |
| WO1996009106A1 (en) * | 1994-09-21 | 1996-03-28 | Industrial Research Limited | Solid-state oxygen ion conductors and oxygen separation device |
| US7407726B2 (en) * | 2003-09-16 | 2008-08-05 | The Gillette Company | Primary alkaline battery containing bismuth metal oxide |
| US7537863B2 (en) * | 2003-09-16 | 2009-05-26 | The Gillette Company | Primary alkaline battery containing bismuth metal oxide |
| US7300722B2 (en) * | 2005-04-11 | 2007-11-27 | The Gillette Company | Lithium battery containing bismuth metal oxide |
| US7972726B2 (en) * | 2006-07-10 | 2011-07-05 | The Gillette Company | Primary alkaline battery containing bismuth metal oxide |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853627A (en) * | 1970-10-29 | 1974-12-10 | Accumulateurs Fixes | Lithium electric cells with novel positive active materials and non-aqueous electrolyte |
| CA970028A (en) * | 1971-02-03 | 1975-06-24 | Bruce H. Garth | High energy density battery |
| FR2169748A1 (en) * | 1972-01-31 | 1973-09-14 | Accumulateurs Fixes | Electrochemical cell - contg lithium anode and an ether-base electrolyte |
| US3736184A (en) * | 1972-03-29 | 1973-05-29 | Mallory & Co Inc P R | Metal phosphate and metal arsenate organic electrolyte cells |
| FR2288401A1 (en) * | 1974-10-17 | 1976-05-14 | Accumulateurs Fixes | ELECTROCHEMICAL GENERATOR |
| JPS5184035A (en) * | 1975-01-20 | 1976-07-23 | Japan Storage Battery Co Ltd | |
| DE2516704C3 (en) * | 1975-04-16 | 1981-07-02 | Varta Batterie Ag, 3000 Hannover | Galvanic element with a negative electrode made of light metal, a non-aqueous electrolyte and a positive electrode |
-
1977
- 1977-10-14 FR FR7730946A patent/FR2406312A1/en active Granted
-
1978
- 1978-09-14 US US05/942,291 patent/US4158723A/en not_active Expired - Lifetime
- 1978-10-04 IT IT69294/78A patent/IT1108107B/en active
- 1978-10-06 EP EP78101086A patent/EP0001598B1/en not_active Expired
- 1978-10-06 DE DE7878101086T patent/DE2860549D1/en not_active Expired
- 1978-10-11 JP JP53124221A patent/JPS5935148B2/en not_active Expired
- 1978-10-11 NZ NZ188630A patent/NZ188630A/en unknown
- 1978-10-12 NO NO783463A patent/NO149299C/en unknown
- 1978-10-12 CA CA313,192A patent/CA1096442A/en not_active Expired
- 1978-10-12 BR BR7806748A patent/BR7806748A/en unknown
- 1978-10-12 AU AU40656/78A patent/AU516528B2/en not_active Expired
- 1978-10-13 IE IE2042/78A patent/IE47359B1/en unknown
- 1978-10-13 ES ES474185A patent/ES474185A1/en not_active Expired
- 1978-10-13 DK DK458278A patent/DK458278A/en not_active Application Discontinuation
-
1983
- 1983-12-09 SG SG786/83A patent/SG78683G/en unknown
-
1984
- 1984-03-16 JP JP59052054A patent/JPS59201369A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NZ188630A (en) | 1980-09-12 |
| JPS5935148B2 (en) | 1984-08-27 |
| IE47359B1 (en) | 1984-02-22 |
| NO149299C (en) | 1984-03-21 |
| EP0001598B1 (en) | 1981-03-18 |
| BR7806748A (en) | 1979-06-26 |
| FR2406312A1 (en) | 1979-05-11 |
| IT1108107B (en) | 1985-12-02 |
| EP0001598A1 (en) | 1979-05-02 |
| NO149299B (en) | 1983-12-12 |
| DK458278A (en) | 1979-04-15 |
| IE782042L (en) | 1979-04-14 |
| NO783463L (en) | 1979-04-18 |
| ES474185A1 (en) | 1979-06-16 |
| SG78683G (en) | 1985-12-13 |
| FR2406312B1 (en) | 1980-04-04 |
| JPS59201369A (en) | 1984-11-14 |
| US4158723A (en) | 1979-06-19 |
| AU4065678A (en) | 1980-04-17 |
| JPS5465334A (en) | 1979-05-25 |
| IT7869294A0 (en) | 1978-10-04 |
| DE2860549D1 (en) | 1981-04-16 |
| AU516528B2 (en) | 1981-06-04 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19980224 |